Photoinduced decatungstate-catalyzed C(sp3)-H thioetherification by sulfinate salts.

Thiols and thioesters play crucial roles in pharmaceuticals, biology, and material science as essential organosulfur compounds. Leveraging readily available and cost-effective inert alkanes through direct thioetherification holds promise for yielding high-value-added products. Herein, we present a photoinduced strategy for sulfur-containing modification of inert alkanes utilizing decatungstate as hydrogen atom transfer reagent, offering a straightforward and practical approach for synthesizing thioethers and thioesters.

Iron-Catalyzed C(Sp3)-H Borylation, Thiolation, and Sulfinylation Enabled by Photoinduced Ligand-to-Metal Charge Transfer.

Catalytic C(sp3)-H functionalization has provided enormous opportunities to construct organic molecules, facilitating the derivatization of complex pharmaceutical compounds. Within this framework, direct hydrogen atom transfer (HAT) photocatalysis becomes an appealing approach to this goal. However, the viable substrates utilized in these protocols are limited, and the site selectivity shows preference to activated and thermodynamically favored C(sp3)-H bonds. Herein, we describe the development of undirected iron-catalyzed C(sp3)-H borylation, thiolation, and sulfinylation reactions enabled by the photoinduced ligand-to-metal charge transfer (LMCT) process. These reactions exhibit remarkably broad substrate scope (>150 examples in total), and most importantly, all of these three reactions show unconventional regioselectivity, with the occurrence of C(sp3)-H borylation, thiolation, and sulfinylation preferentially at the distal methyl position. The procedures are operationally simple and readily scalable and provide access to high-value products from simple hydrocarbons in one step. Mechanistic studies and control experiments indicate that the afforded site selectivity is not only relevant to the HAT species but also largely affected by the use of boron- and sulfone-based radical acceptors.

Iron-Catalyzed Multicomponent C-H Alkylation of in Situ Generated Imines via Photoinduced Ligand-to-Metal Charge Transfer.

Herein, we describe a novel photoinduced iron-catalyzed strategy for multicomponent C-H alkylation of in situ generated imines. By utilizing the alkyl radicals generated through iron-mediated photocatalytic C-H activation, the imines formed in situ are further subjected to addition reactions, resulting in the synthesis of various secondary and tertiary amine products. This method is simple to operate and does not require additional oxidants. It is applicable to inert alkane substrates such as cyclic alkanes, cyclic ethers, toluene, and ketones. The reaction is also compatible with various aromatic amines, alkyl amines, halogenated aromatic amines, as well as aromatic aldehydes, alkyl aldehydes, and cinnamaldehyde, among other different types of aldehydes.